CN104817222A - Waste water treatment method and waste water treatment device - Google Patents
Waste water treatment method and waste water treatment device Download PDFInfo
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- CN104817222A CN104817222A CN201510041836.0A CN201510041836A CN104817222A CN 104817222 A CN104817222 A CN 104817222A CN 201510041836 A CN201510041836 A CN 201510041836A CN 104817222 A CN104817222 A CN 104817222A
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- activated sludge
- wastewater treatment
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- 239000012528 membrane Substances 0.000 claims abstract description 184
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- 238000000034 method Methods 0.000 claims abstract description 145
- 239000010802 sludge Substances 0.000 claims abstract description 94
- 238000000926 separation method Methods 0.000 claims abstract description 77
- 239000002351 wastewater Substances 0.000 claims abstract description 59
- 238000001914 filtration Methods 0.000 claims abstract description 48
- 244000005700 microbiome Species 0.000 claims abstract description 27
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- 230000000813 microbial effect Effects 0.000 claims description 32
- 238000001728 nano-filtration Methods 0.000 claims description 28
- 238000001223 reverse osmosis Methods 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 238000005374 membrane filtration Methods 0.000 claims description 18
- 238000001704 evaporation Methods 0.000 claims description 15
- 230000008020 evaporation Effects 0.000 claims description 13
- 238000003672 processing method Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 30
- 238000002156 mixing Methods 0.000 description 27
- 150000001409 amidines Chemical class 0.000 description 12
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- 102000010637 Aquaporins Human genes 0.000 description 5
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- 238000005276 aerator Methods 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
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- 125000004093 cyano group Chemical group *C#N 0.000 description 2
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- 238000010438 heat treatment Methods 0.000 description 2
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- 238000001471 micro-filtration Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
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- 238000001179 sorption measurement Methods 0.000 description 2
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical compound NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
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- 229920001155 polypropylene Polymers 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
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- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
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- 238000011144 upstream manufacturing Methods 0.000 description 1
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Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The task of the invention is to provide a waste water treatment method and a waste water treatment device which can obtain high-quality treated water and suppress membrane obstruction of a filtering membrane in treating of treated water which has been subjected to a membrane separating activated sludge process. The solution of the invention is the waste water treatment method and the waste water treatment device. According to the waste water processing method, an agglutinant is added into a membrane separating groove 11 through an agglutinant adding device 16 and by means of a membrane separating activated sludge treatment device 10 to treat waste water. In the membrane separating activated sludge treatment device 10, biological treating carried out through microorganisms in the activated sludge and solid-liquid separation treating carried out through a membrane assembly 15 proceed in the same a membrane separating groove 11. Further treatment is carried out on membrane separating treated water which has been subjected to solid-liquid separation treating by the membrane separating activated sludge treatment device 10 through a biological membrane treatment device 70 which carries out biological processing through microorganisms attached on supporters.
Description
Technical field
The present invention relates to method of wastewater treatment and be applicable to the wastewater treatment equipment of this method of wastewater treatment.
Background technology
To sanitary wastewater or trade effluent implement that removing wherein contains be suspended the process of material or organism etc. after, drain in river etc.
In the treatment process of the waste water containing organism etc., compared to conventional actived sludge in the past, membrane separation activated sludge process (MBR) is a kind of effective means.Here, MBR refers to, does not arrange final settling bath but carried out the method for solid-liquid separation by separatory membrane in activated sludge process.
A kind ofly to be proposed (such as with reference to patent documentation 1) in the method by adding amidine system agglutinant during MBR process waste water.While agglutinant is adsorbed on Sludge Surface, also live decomposing the Adsorption of Organics such as the hardly-degradable substance of difficulty in MBR.
Look-ahead technique document
Patent documentation
No. 2011/016482nd, [patent documentation 1] International Publication
Summary of the invention
The problem that the present invention will solve
But excessive interpolation agglutinant or sludge quantity less relative to the amount of agglutinant time, agglutinant process water in remaining.Because agglutinant is organism, so agglutinant becomes the pollution cause of process water.That is, the BOD of water is processed
5or COD
crrise, the water quality deterioration of process water.
In addition, when filtration treatment being carried out to process water by reverse osmosis membrane or nano-filtration membrane etc., if in process water hardly-degradable substance or agglutinant remaining, the risk that hardly-degradable substance or agglutinant will be had to cause the film of filtering membrane block.
The present invention take said circumstances as the invention that mirror completes, though problem of the present invention be to provide a kind of can obtain high water quality process water and the method for wastewater treatment that the film of filtering membrane also can be suppressed to block when carrying out filtration treatment to the process water after membrane separation activated sludge process process and wastewater treatment equipment.
Solve the method for problem
The present invention has following form.
[1] a kind of method of wastewater treatment, in groove, agglutinant is added and after processing waste water by membrane separation activated sludge process, by biomembrance process, the membrane separation water through described membrane separation activated sludge process solid-liquid separation is further processed, in described membrane separation activated sludge process, the biological treatment of the microorganism in active sludge and the solid-liquid separation process of separatory membrane are carried out in same described groove, in described biomembrance process, carried out a biological disposal upon by the microorganism be attached on carrier.
[2] according to the method for wastewater treatment recorded in [1], the BOD of described membrane separation water
5/ COD
crbelow 0.3.
[3] according to the method for wastewater treatment recorded in [1] or [2], biomembrance process is biological activated carbon treatment method.
[4] method of wastewater treatment, carrys out by reverse osmosis membrane or nano-filtration membrane the microbial film process water that filtration treatment obtained by the method for wastewater treatment described in any one of [1] ~ [3].
[5] method of wastewater treatment Gen Ju [4], carries out concentration to the condensed water produced by described filtration treatment.
[6] a kind of wastewater treatment equipment, it possesses film separated activated sludge treatment unit and biofilm treatment apparatus, in described film separated activated sludge treatment unit, the biological treatment of the microorganism in active sludge and the solid-liquid separation process of separatory membrane are carried out in same groove, in described biofilm treatment apparatus, carried out a biological disposal upon to the membrane separation water through described film separated activated sludge treatment unit solid-liquid separation by the microorganism be attached on carrier, described film separated activated sludge treatment unit has the agglutinant adding set adding agglutinant in described groove.
[7] according to the wastewater treatment equipment recorded in [6], the BOD of described membrane separation water
5/ CODcr is below 0.3.
[8] according to the wastewater treatment equipment recorded in [6] or [7], biofilm treatment apparatus is biological activated carbon treatment device.
[9] according to the wastewater treatment equipment described in any one of [6] ~ [8], described wastewater treatment equipment also possesses reverse osmosis membrane filtration device or nanofiltration membrane filter appts, and described reverse osmosis membrane filtration device or nanofiltration membrane filter appts carry out filtration treatment to microbial film process water treated in biofilm treatment apparatus.
[10] wastewater treatment equipment Gen Ju [9], described wastewater treatment equipment also possesses evaporation concentration device, and described evaporation concentration device carries out concentration to the condensed water produced by described reverse osmosis membrane filtration device or nanofiltration membrane filter appts.
The effect of invention
According to method of wastewater treatment of the present invention and wastewater treatment equipment, the process water of high water quality can be obtained, even and if the film of filtering membrane also can be suppressed to block when carrying out filtration treatment to the process water after membrane separation activated sludge process process.
Accompanying drawing explanation
[Fig. 1] shows the structural representation of an embodiment of wastewater treatment equipment of the present invention.
[Fig. 2] shows the structural representation of other embodiments of wastewater treatment equipment of the present invention.
Nomenclature
10 film separated activated sludge treatment unit
11 membrane sepn grooves
15 membrane modules
16 agglutinant adding sets
20 standard activated sludge treatment unit
30 filtration units
40 evaporation concentration devices
70 biofilm treatment apparatus
Embodiment
(method of wastewater treatment)
Method of wastewater treatment of the present invention is when processing waste water by membrane separation activated sludge process (MBR), adds the method for agglutinant in the groove carrying out processing (membrane sepn groove).
Below, be that the present invention will be described for example in particular embodiments.
The embodiment > of < wastewater treatment equipment
Fig. 1 is the structural representation of an embodiment of display wastewater treatment equipment of the present invention.
This wastewater treatment equipment possesses film separated activated sludge treatment unit 10 and biofilm treatment apparatus 70, this film separated activated sludge treatment unit 10 is while carrying out a biological disposal upon to the waste water from former tank (omitting diagram) by the microorganism in active sludge, also by being treated to mud and membrane separation water (infiltration water) as membrane module 15 solid-liquid separation of separatory membrane, biofilm treatment apparatus 70 is carried out a biological disposal upon to the membrane separation water through film separated activated sludge treatment unit 10 solid-liquid separation by the microorganism be attached on carrier.
(film separated activated sludge treatment unit)
Film separated activated sludge treatment unit 10 possesses: membrane sepn groove (the 1st aerator tank) 11; Be configured in the diffuser 12 near the bottom in membrane sepn groove 11; Air fed fan 13 in diffuser 12; Connect the air leading-in conduit 14 of diffuser 12 and fan 13; To be configured in membrane sepn groove 11 and the membrane module 15 be positioned at above diffuser 12; The agglutinant adding set 16 of agglutinant is added in membrane sepn groove 11; Being arranged at the midway of membrane separation Aquaporin-5 1, by carrying out the solid-liquid separation of mud and membrane separation water (infiltration water) to decompression in membrane module 15, and membrane separation water being delivered to the off-gas pump 18 of biofilm treatment apparatus 70; Waste water from former tank is supplied to the supply waste water tunnel 50 of film separated activated sludge treatment unit 10; By the membrane separation Aquaporin-5 1 that the membrane separation water from film separated activated sludge treatment unit 10 is discharged; By the excess sludge passage 52 that the excess sludge from film separated activated sludge treatment unit 10 is discharged.
As membrane module 15, for example there are the known membrane module with known filtering membrane.
As the kind of filtering membrane, preferred microfiltration membrane (MF film) or ultra-filtration membrane (UF film).As the shape of filtering membrane, for example there are hollow fiber membrane, flat film, tubular film, bag-shaped film etc.Among these, consider when comparing based on volume, the height aggregation of membrane area may be had, then preferred hollow fiber membrane.
As the material of filtering membrane, for example there are: organic materials (Mierocrystalline cellulose, polyolefine, polysulfones, polyvinyl alcohol, polymethylmethacrylate, polyvinylidene difluoride (PVDF), tetrafluoroethylene etc.), metal (stainless steel etc.), inorganic materials (pottery etc.).The material of filtering membrane can do suitable selection according to waste water proterties.
The aperture of filtering membrane, can do suitable selection according to the object of process.In MBR, preferably 0.001 ~ 3 μm, the aperture of filtering membrane.If aperture is more than 0.001 μm, then the resistance of film can be suppressed to become large.If aperture is below 3 μm, can isolating active mud fully, maintain the water quality of good process water.The aperture of filtering membrane, during scope as microfiltration membrane then more preferably 0.04 ~ 1.0 μm.
Can use diffuser 12 film unit integrated with membrane module 15 in film separated activated sludge treatment unit 10.As such film unit, the film unit etc. of citing as recorded in Japanese Patent Laid-Open 2013-202524 publication.
Agglutinant adding set 16 has: agglutinant is supplied to the agglutinant passage 16a in membrane sepn groove 11; Be arranged at the midway of agglutinant passage 16a, agglutinant be delivered to the pump 16b of membrane sepn groove 11.
(biofilm treatment apparatus)
Biofilm treatment apparatus 70 has: microbial film groove (the 2nd aerator tank) 71; Be configured at the diffuser 72 near the bottom in microbial film groove 71; Air fed fan 73 in diffuser 72; Connect the air leading-in conduit 74 of diffuser 72 and fan 73; By the microbial film process aquaporin 62 that the microbial film process water of carrying out a biological disposal upon through microbial film groove 71 is discharged.
In microbial film groove 71, accommodate the microorganic adhesion carrier (omitting diagram) of the carrier being attached with microorganism.
Microorganic adhesion carrier, can make it flow in microbial film groove 71, it also can be made to fix.Microorganic adhesion carrier is made on limit to flow in microbial film groove 71, while the biofilm treatment apparatus 70 carrying out carrying out a biological disposal upon is called fluidized bed-type biofilm treatment apparatus, military order microorganic adhesion carrier is fixed in microbial film groove 71 biofilm treatment apparatus 70 carrying out carrying out a biological disposal upon and is called fixed-bed type biofilm treatment apparatus.
As carrier, for example there are fixed bed carrier, thermopnore carrier etc.
Such as thermopnore carrier, for example there are gac etc.In addition, as thermopnore carrier, except gac, the resin-made such as polypropylene or polyvinyl alcohol carrier, pottery carrier processed etc. can also be used.Wherein, when considering as microorganic adhesion carrier, the excellent this point of the decomposition of reluctant hardly-degradable substance or agglutinant in membrane separation activated sludge process, preferred gac.Here, the biofilm treatment apparatus 70 that microorganic adhesion microorganic adhesion carrier is on the activated carbon accommodated in microbial film groove 71 is called biological activated carbon treatment unit.
(standard activated sludge treatment unit)
Wastewater treatment equipment, as shown in Figure 2, can possess standard activated sludge treatment unit 20 in the upstream of film separated activated sludge treatment unit 10 further, standard activated sludge treatment unit 20 is carried out a biological disposal upon to the waste water from former tank (omitting diagram) by the microorganism in active sludge.
In addition, in Fig. 2, the component identical with Fig. 1 denotes identical symbol, omit its description.
Standard activated sludge treatment unit 20 has: activated sludge tank (the 3rd aerator tank) 21; Be configured at the diffuser 22 of the close bottom in activated sludge tank 21; Air fed fan 23 in diffuser 22; Connect the air leading-in conduit 24 of diffuser 22 and fan 23; To be the settling bath 25 of mud and supernatant liquor through the activated sludge tank mixing water solid-liquid separation of biological treatment in activated sludge tank 21; Waste water from former tank is supplied to the waste water tunnel 50 of activated sludge tank 21; By the activated sludge tank mixing water passage 53 be transplanted on through the activated sludge tank mixing water of biological treatment in activated sludge tank 21 in settling bath 25; The supernatant liquor of autoprecipitation groove 25 is transferred to the supernatant liquor passage 54 of film separated activated sludge treatment unit 10 in the future; By the excess sludge passage 55 that excess sludge is discharged from settling bath 25; A part for excess sludge is returned to from settling bath 25 the foldback mud passage 56 of activated sludge tank 21.
As long as it is mud and supernatant liquor and passable that settling bath 25 can make to transfer the activated sludge tank mixing water solid-liquid separation of coming by activated sludge tank 21 by gravitational settling, it is had no particular limits.Settling bath 25 can be general settling tank.
(filtration unit)
Wastewater treatment equipment, as shown in Figure 2, can also possess filtration unit 30 further, and through biological treatment in filtration unit 30 pairs of microbial film grooves 71, the microbial film process water of discharging from microbial film process aquaporin 62 carries out filtration treatment.
Filtration unit 30 has: filtration unit main body 31; By the pure water passage 58 that the pure water through filtration unit main body 31 is discharged; By the condensed water passage 59 that the condensed water not through filtration unit main body 31 is discharged.
As filtration unit main body 31, for example there are the filtration unit main body with reverse osmosis membrane assembly or nano-filtration membrane module., the filtration unit 30 with reverse osmosis membrane assembly as filtration unit main body 31 is called reverse osmosis membrane filtration device here, the filtration unit 30 with nano-filtration membrane module as filtration unit main body 31 is called nanofiltration membrane filter appts.
As long as pure water and the condensed water not through reverse osmosis membrane through reverse osmosis membrane can be carried out the form that is separated and passable by reverse osmosis membrane assembly, it is not particularly limited.
As reverse osmosis membrane assembly, citing is as so-called spiral type reverse osmosis membrane assembly etc., and reverse osmosis membrane is received in cylindric sleeve pipe at the columned reverse-osmosis membrane element that the side face of header is wound into by it.
As the material of reverse osmosis membrane, for example there are polymeric amide, polysulfones, cellulose acetate etc., preferably contain the polymeric amide of aromatic polyamide or crosslinked aromatic polymeric amide.
As long as pure water and the condensed water not through nano-filtration membrane through nano-filtration membrane can be carried out the form that is separated and passable by nano-filtration membrane module, it is not particularly limited.
As nano-filtration membrane module, citing is as so-called spiral type nano-filtration membrane module etc., and nano-filtration membrane is received in cylindric sleeve pipe at the columned nanofiltration membrane element that the side face of header is wound into by it.
As the material of nano-filtration membrane, what for example there are containing polyethylene-based, aromatic polyamide system or crosslinked polyamide system is polyamide-based, aliphatic amide polycondensate, heterocycle polymer system, polyethenol series, cellulose acetate based polymer etc.
(evaporation concentration device)
Wastewater treatment equipment, as shown in Figure 2, can also possess evaporation concentration device 40 further, evaporation concentration device 40 carries out concentration to the condensed water not through filtration unit main body 31.
Evaporation concentration device 40 has: vaporizer 41; By the condensed water passage 60 that the condensed water of evaporating in vaporizer 41, condensing is discharged; By the thickened waste aquaporin 61 that concentrated waste water concentrated in vaporizer 41 is discharged.
As long as vaporizer 41 can carry out heating concentrated form and passable to condensed water, it is not particularly limited.
The embodiment > of < method of wastewater treatment
Use the method for wastewater treatment of the wastewater treatment equipment of Fig. 1, there is following step (b), (c), use the method for wastewater treatment of the wastewater treatment equipment of Fig. 2 to have following step (b), (c), as required there is following (a), (d), (e).
In (a) standard activated sludge treatment unit 20, the step of the waste water from former tank (omitting diagram) being carried out a biological disposal upon by the microorganism in active sludge.
In (b) film separated activated sludge treatment unit 10, while treated waste water (supernatant liquor) in from the waste water of former tank (omitting diagram) or step (a) being carried out a biological disposal upon by the microorganism in active sludge, be mud and the step of process water (infiltration water) by membrane module 15 solid-liquid separation.
In (c) biofilm treatment apparatus 70, to the step that the separatory membrane process water (infiltration water) through membrane module 15 is carried out a biological disposal upon.
In (d) filtration unit 30, by reverse osmosis membrane or nano-filtration membrane, the step of filtration treatment is carried out to the microbial film process water through carrying out a biological disposal upon in microbial film groove 71.
In (e) evaporation concentration device 40, the condensed water not through filtration unit main body 31 is carried out to the step of concentration.
(waste water)
In wastewater treatment equipment, treated waste water is usually containing the organism such as easy decomposability material or hardly-degradable substance.As such waste water, citing is as sanitary wastewater, trade effluent (chemistry, pharmacy, papermaking, beverage, oil refining, semi-conductor, electronics etc.), farm waste water etc.
Thick seston, native sand etc. can be removed in advance to waste water, adjust its pH, dilution.
(step (a))
Treated waste water in step (b), also can process in advance in standard activated sludge treatment unit 20.
In step (a), first the waste water be stored in former tank (omitting diagram) is supplied in the activated sludge tank 21 of standard activated sludge treatment unit 20 via waste water tunnel 50.
In activated sludge tank 21, fan 23 is operated, by diffuser 22 introducing air, by supplying oxygen supply to the microorganism in active sludge thus carrying out the biological treatment of waste water.
Then, be delivered in activated sludge tank 21 in settling bath 25 via activated sludge tank mixing water passage 53 through the activated sludge tank mixing water of biological treatment.
In settling bath 25, be mud and supernatant liquor by gravitational settling by activated sludge tank mixing water solid-liquid separation.
The supernatant liquor of settling bath 25, as waste water treated in step (b), is transported in film separated activated sludge treatment unit 10 via supernatant liquor passage 54.
On the other hand, isolated excess sludge is discharged via excess sludge passage 55.In addition, because comprise microorganism in excess sludge, so a part for excess sludge can be returned in activated sludge tank 21, again for the biological treatment of waste water via foldback mud passage 56.
(step (b))
When method of wastewater treatment does not have step (a), the waste water be stored in former tank (omitting diagram) is supplied in the membrane sepn groove 11 of film separated activated sludge treatment unit 10 via waste water tunnel 50.
When method of wastewater treatment has step (a), waste water (supernatant liquor) treated in step (a) is supplied in the membrane sepn groove 11 of film separated activated sludge treatment unit 10 via supernatant liquor passage 54.
In membrane sepn groove 11, fan 13 is operated, by diffuser 12 introducing air, by supplying oxygen supply to the microorganism in active sludge thus carrying out the biological treatment of waste water.
In addition, in membrane sepn groove 11, by making off-gas pump 18 operate decompression in membrane module 15, be mud and process water (infiltration water) by mixing water solid-liquid separation.Now, by diffuser 12, air is imported in membrane module 15, can the surface of separatory membrane (such as hollow fiber membrane etc.) of limit washing membrane module 15, solid-liquid separation is carried out efficiently in limit.
In step (b), in membrane sepn groove 11, add agglutinant by agglutinant adding set 16 and waste water is processed.
The addition of agglutinant, as long as can the amount of organism (particularly hardly-degradable substance) in aggegation waste water just be not particularly limited.
In step (b), preferably treatment waste water makes the BOD of the separatory membrane process water (infiltration water) through membrane module 15
5/ COD
crbe less than 0.3, more preferably process the BOD that waste water makes the separatory membrane process water (infiltration water) through membrane module 15
5/ COD
crbe less than 0.3 and SS concentration is below 25mg/L.
The BOD of separatory membrane process water
5/ COD
crif below 0.3, the concentration (COD of the hardly-degradable substance in the microbial film process water in step (c) after biological treatment
cr-BOD
5) more reduce.Therefore, the process water of higher water quality can be obtained.And when carrying out filtration treatment to microbial film process water in step (d), the film of reverse osmosis membrane or the such filtering membrane of nano-filtration membrane more can be suppressed to block.
If the SS concentration of separatory membrane process water is at below 25mg/L, the biological treatment in step (c) can be carried out more smoothly.Particularly, when being carried out a biological disposal upon by biological activated carbon facture in step (c), if the SS concentration of separatory membrane process water is at below 25mg/L, can the blocking of inhibit activities charcoal, so biological treatment can more successfully be carried out.
The BOD of separatory membrane process water
5/ COD
crand SS concentration, can be adjusted by the addition of the residence time in membrane sepn groove 11 or agglutinant.Such as, the residence time in membrane sepn groove 11 is longer, and the addition of agglutinant is more, then the BOD of separatory membrane process water
5/ COD
crand SS concentration more has the tendency diminished.In addition, even if carried out step (a), the BOD of separatory membrane process water before step (b)
5/ COD
cralso the tendency diminished is had.
In addition, " COD
cr" be the oxygen-consumption of potassium bichromate, measure according to JIS K 0102.
In addition, " BOD
5" be the biochemical oxygen demand (BOD) of 5 days, measure according to JIS K 0102.
In addition, the concentration that " SS concentration " is the suspended solid in water, measures according to JIS K 0102.
Be not particularly limited as the agglutinant used in step (b), preferred polymer coagulant.Polymer coagulant has the effect by making micro clots be cross-linked to form thick grumeleuse.In addition, polymer coagulant, according to the adsorption activity group that agglutinant has, has nonionic system, negatively charged ion system and positively charged ion system etc.Particularly from processing efficiency aspect, as the agglutinant used in step (b), the amidine system agglutinant that the cationic polymer preferably with following formula (1) and/or the amidine structural unit shown in (2) contains as its effective constituent.
In addition, in the present invention, " effective constituent " means the polymeric content of cationic in 100 quality % agglutinants, usually preferably containing 10 ~ 100 quality %.
[changing 1]
In formula (1), (2), R
1~ R
4be respectively hydrogen atom or methyl, can be identical or different.
X
-, Y
-be respectively negatively charged ion, can be identical or different.As negatively charged ion, citing is as Cl
-, BR
-, 1/2SO
4 2 -, CH
3(CO) O
-, H (CO) O
-deng.Wherein preferred Cl
-.
Be not particularly limited as the polymeric manufacture method of such cationic, be exemplified below the method for stating, manufacture the multipolymer that there is primary amine groups or the ethylene unsaturated monomer of the substituted-amino of primary amine groups and the nitrile of vinyl cyanide or methacrylonitrile can be generated by conversion reaction, after acid hydrolysis, the cyano group in this multipolymer and primary amine groups are reacted and the method for amidineization.
Cationic polymer, preferably by most typical following method manufacture, make N-vinyl formamide and acrylonitrile compolymer, under the existence of aqeous suspension hydrochloric acid, usually heat the multipolymer of generation, form amidine structural unit by the cyano group adjacent with substituted-amino and manufacture.Like this, according to for the N-vinyl formamide of copolymerization and the mol ratio of vinyl cyanide, and the amidineization condition of selected multipolymer can obtain the cationic polymer of various composition.
For cationic polymer, in this cationic polymer 100 % by mole, preferably containing 5 ~ 90 % by mole of above-mentioned formulas (1) and/or the amidine structural unit represented by (2) as repeating unit.When the containing ratio of amidine structural unit is less than 5 % by mole, because the content of amidine structural unit very little, when this cationic polymer uses as agglutinant, its usage quantity can become many.On the other hand, the cationic polymer of containing ratio more than 90 % by mole of amidine structural unit, is difficult to by manufacturing in aforesaid method.The lower value of the containing ratio of amidine structural unit, more preferably more than 10 % by mole, preferably more than 15 % by mole further, particularly preferably more than 20 % by mole.In addition, the higher limit of the containing ratio of amidine structural unit, more preferably less than 85 % by mole, preferably less than 80 % by mole further.
In addition, when cationic polymer is manufactured by aforesaid method, except described amidine structural unit, sometimes also containing the unit represented by following formula (3) ~ (5).
[changing 2]
In formula (3) ~ (5), R
5, R
7, R
8be respectively hydrogen atom or methyl, can be identical or different.
R
6alkyl or the hydrogen atom of carbonatoms 1 ~ 4.
Z
-it is negatively charged ion.As negatively charged ion, identical with the negatively charged ion that example is crossed in the explanation of above-mentioned formula (1), (2) above.
When cationic polymer contains the unit represented by above-mentioned formula (3) ~ (5), usually, in this cationic polymer 100 % by mole, containing the repeating unit 0 ~ 40 % by mole represented by above-mentioned formula (3), repeating unit represented by above-mentioned formula (4) 0 ~ 70 % by mole, the repeating unit represented by above-mentioned formula (5) 0 ~ 70 % by mole.
Above-mentioned formula (1) and/or the amidine structural unit represented by (2), and the composition of unit represented by above-mentioned formula (3) ~ (5), can be polymerized mol ratio by ethylene unsaturated monomer and nitrile, or the condition (temperature or time) of amidineization reaction adjusts.
In addition, these compositions can be polymeric by measuring cationic
13c-NMR (
13c-nucleus magnetic resonance) obtain, particularly, by corresponding with each repeating unit
13the integrated value at the peak (signal) of C-NMR spectrum calculates.
(step (c))
Through the membrane separation water (infiltration water) of membrane module 15, be supplied in biofilm treatment apparatus 70 via membrane separation Aquaporin-5 1.
In microbial film groove 71, fan 73 is operated, by diffuser 72 introducing air, by carrying out the biological treatment of membrane separation water to the microorganism oxygen supply be attached on carrier.By this biological treatment, the organism such as the agglutinant in membrane separation water or hardly-degradable substance are decomposed by the microorganisms.
Consider from decomposition this point excellent of hardly-degradable substance or agglutinant, preferably use biological activated carbon treatment unit to be carried out a biological disposal upon to membrane separation water by biological activated carbon facture as biofilm treatment apparatus 70.
(step (d))
In step (c), although directly outside can be discharged into through the microbial film process water of biological treatment in microbial film groove 71, but be preferably delivered to filtration unit 30 via microbial film process aquaporin 62, carry out filtration treatment by reverse osmosis membrane or nano-filtration membrane.
In filtration unit 30, the process water through reverse osmosis membrane or nano-filtration membrane becomes pure water, is discharged by pure water passage 58.On the other hand, the process water not through reverse osmosis membrane or nano-filtration membrane becomes condensed water, is discharged by condensed water passage 59.
(step (e))
In step (d), less than the process water (condensed water) through reverse osmosis membrane or nano-filtration membrane although directly outside can be discharged into, be preferably delivered to evaporation concentration device 40 via condensed water passage 59, carry out concentration.
In evaporation concentration device 40, deliver to the condensed water in vaporizer 41, evaporate after being omitted the heating of illustrated heat transmitter, become water vapour.Water vapour condenses after being omitted the cooling of illustrated water cooler, becomes condensed water, is discharged by condensed water passage 60.The condensed water be concentrated in vaporizer 41 is discharged by thickened waste aquaporin 61 as concentrated waste water.
When concentration being carried out to condensed water in evaporation concentration device 40, in order to the corrosion of the concentrating unit 40 that avoids evaporating, the alkali such as sodium hydroxide can be added in condensed water.
Although concentrated waste water can directly be discharged to the outside, the state with solid matter after being usually dried is discharged.
(action effect)
In above-mentioned illustrated method of wastewater treatment of the present invention and wastewater treatment equipment, after adding agglutinant process waste water by MBR, by biomembrance process, further process is done to the membrane separation water through solid-liquid separation in MBR.Therefore, even if be less than the amount of agglutinant thus agglutinant is remaining in membrane separation water because of the amount of excessive interpolation agglutinant or mud, agglutinant can be removed from membrane separation water by biomembrance process.In addition, biomembrance process can also will decompose the organism removings such as the hardly-degradable substance of difficulty in MBR.Therefore, treated microbial film process water in biomembrance process, its BOD
5, COD
cr, hardly-degradable substance concentration (COD
cr-BOD
5) low, the process water of high water quality can be obtained.
And, because agglutinant or hardly-degradable substance can be removed by biomembrance process, even if so when carrying out filtration treatment by reverse osmosis membrane or nano-filtration membrane etc. to microbial film process water, the film of filtering membrane also can be suppressed to block.
[embodiment]
Below, according to embodiment, more specific description is done to the present invention, but the present invention is not limited thereto.
(agglutinant)
As agglutinant, use poly-amidine system polymer coagulant (Mitsubishi Rayon Co., Ltd's system, " KP7000 ").
(example 1 ~ 5)
As the waste water containing hardly-degradable substance, use the waste water of discharging from coke manufacturing process.Known waste water (coke waste water) of discharging from coke manufacturing process containing humic substance etc., the hardly-degradable substance containing more general biological treatment difficulty.
The COD of the waste water used in this example
crfor 3500mg/L, BOD
5for 500mg/L.Therefore, the concentration (COD of the hardly-degradable substance in waste water
cr-BOD
5) be 3000mg/L, BOD
5/ COD
crbe 0.14.In addition, COD
crand BOD
5measure according to JIS K 0102.
The process > that < carries out according to membrane separation activated sludge process
(preparation of membrane separation water (I))
Waste water is processed by membrane separation activated sludge process (MBR), MLSS concentration is used to be adjusted to active sludge and hollow fiber membrane (Mitsubishi Rayon Co., Ltd's system of 8000mg/L in described membrane separation activated sludge process, " ス テ ラ Port ア SADF "), obtain membrane separation water (I).In process, be set as aerobic condition from the below aeration of hollow fiber membrane, the hydraulic residence time is 24 hours.
The COD of the membrane separation water (I) obtained is measured according to JIS K 0102
crand BOD
5, COD
crfor 2000mg/L, BOD
5for 50mg/L, the concentration (COD of hardly-degradable substance
cr-BOD
5) be 1950mg/L.
(preparation of membrane separation water (II))
Except adding agglutinant continuously until except 500mg/L in waste water, processing waste water under the condition identical with the preparation of membrane separation water (I), obtaining membrane separation water (II).
The COD of the membrane separation water (II) obtained is measured according to JIS K 0102
crand BOD
5, COD
crfor 1500mg/L, BOD
5for 50mg/L, the concentration (COD of hardly-degradable substance
cr-BOD
5) be 1450mg/L.
The process > that < carries out according to biomembrance process
Membrane separation water (II) (COD
cr=1500mg/L, BOD
5=50mg/L, COD
cr-BOD
5=1450mg/L), sanitary wastewater (COD
cr=500mg/L, BOD
5=425mg/L, COD
cr-BOD
5=75mg/L, BOD
5/ COD
cr=0.85) mix with pure water as mixing former water.The blending ratio of membrane separation water (II), sanitary wastewater and pure water is make the COD in the former water of mixing
cr, BOD
5/ COD
cr, and SS concentration be the corresponding value of the value shown in table 1.Mix the BOD in former water
5and COD
cr-BOD
5also displayed in Table 1 in the lump.In addition, SS concentration measures according to JIS K 0102.
While make to be filled with 200mL gac (Mitsubishi Rayon Co., Ltd's system, " ダ イ ヤ マ Le ス SAC ", effective clearance rate 75%) chromatographic column (diameter 50mm, length 20cm) interior aeration, while enter water to the former water of mixing under the condition of space velocity SV=0.042/hr.In addition, be filled with the chromatographic column of above-mentioned gac, limit makes membrane separation (I) aeration limit intake 1 month under the condition of 0.021/hr in advance, make microorganism adhere on activated carbon surface and breed, carry out cultivating fully becoming microorganism active charcoal (microorganic adhesion carrier) to it.
Take, to the process water (microbial film process water) after 240 hours from water inlet, to measure COD
crand BOD
5, obtain the concentration (COD of hardly-degradable substance in microbial film process water
cr-BOD
5).Result is displayed in Table 1.
In addition, example 1 ~ 5 is equivalent to embodiment.
[table 1]
The result of table 1 clearly shows, and is processed the former water of mixing by biomembrance process, can remove the hardly-degradable substance comprised in the former water of mixing.Particularly, BOD is used
5/ COD
crduring the former water of the mixing below 0.3 (example 1 ~ 3), significantly can remove hardly-degradable substance.This means, BOD
5/ COD
crheight, the ratio mixing the easy decomposability material in former water is large, by biomembrance process to BOD
5/ COD
crwhen the former water of high mixing processes, the easily easy decomposability material of preferential decomposition.Therefore think its with by biomembrance process to BOD
5/ COD
crcompare when the former water of low mixing processes, the concentration of the hardly-degradable substance in microbial film process water uprises.
Learnt by this result, after adding agglutinant process waste water by MBR, water (membrane separation water) is processed further by biomembrance process, the organism such as agglutinant or hardly-degradable substance can be removed from membrane separation water, obtain the process water (microbial film process water) of high water quality.
Usually, commute decomposability material mixes the waste water existed when carrying out carrying out a biological disposal upon with hardly-degradable substance, have the microorganism preferential proliferation decomposing easy decomposability material, and the propagation of decomposing the bacterium of hardly-degradable substance has repressed tendency.According to the present invention, when sewage relatively containing more hardly-degradable substance is carried out a biological disposal upon, the microorganism of decomposing easy decomposed substance does not have preferential proliferation, and the bacterium of decomposing hardly-degradable substance stably breeds, and stably can process hardly-degradable substance thus.
If the particularly BOD of membrane separation water
5/ COD
crbelow 0.3, then hardly-degradable substance is significantly removed, and can obtain the process water of higher water quality.In addition, even if carry out filtration treatment by reverse osmosis membrane or nano-filtration membrane etc. to the microbial film process water obtained, the film of filtering membrane blocks also more easily suppressed.
(example 6 ~ 10)
Membrane separation water (II) (COD
cr=1500mg/L, BOD
5=50mg/L, COD
cr-BOD
5=1450mg/L), sanitary wastewater (COD
cr=500mg/L, BOD
5=425mg/L, COD
cr-BOD
5=75mg/L, BOD
5/ COD
cr=0.85) mix with pure water, as the former water of mixing.The blending ratio of membrane separation water (II), sanitary wastewater and pure water makes the COD in the former water of mixing
crfor 500mg/L, BOD
5for the value of 100mg/L.Adding active sludge further makes the SS concentration mixing former water become value as shown in table 2.
While make to be filled with 200mL gac (Mitsubishi Rayon Co., Ltd's system, " ダ イ ヤ マ Le ス SAC ", effective clearance rate 75%) chromatographic column (diameter 50mm, length 20cm) interior aeration, while enter water to the former water of mixing under the condition of space velocity SV=0.042/hr.In addition, be filled with the chromatographic column of above-mentioned gac, limit makes membrane separation water (I) aeration limit intake 1 month under the condition of 0.021/hr in advance, make microorganism adhere on activated carbon surface and breed, carry out cultivating fully becoming microorganism active charcoal (microorganic adhesion carrier) to it
Measure the distance of the gac upper surface in chromatographic column to the water surface as the pressure used in chromatographic column.Measure time during this distance arrival 20cm.Result is displayed in Table 2.
In addition, example 6 ~ 10 is equivalent to embodiment.
[table 2]
When the pressure used in chromatographic column becomes large, mean the blocking creating gac, usually need the operations such as reverse cleaning.The time when upper surface of the gac in chromatographic column to the distance of the water surface arrives 20cm is longer, then the process of the former water of mixing mean that gac does not block, carrying out according to biomembrance process is successfully carried out.
Result as table 2 clearly shows, and among each example, successfully can be carried out the process of more than 7 hours by biomembrance process to the former water of mixing.Particularly use SS concentration (example 6,7) when the former water of the mixing of below 25mg/L, even if through 240 hours, gac does not also block, and stably can be processed by biomembrance process to the former water of mixing.
Learnt by this result, after adding agglutinant process waste water by MBR, water (membrane separation water) is processed further by biomembrance process, if the SS concentration of membrane separation water is when below 25mg/L, can the blocking of effective inhibit activities charcoal, successfully process membrane separation water.
Claims (10)
1. a method of wastewater treatment, described method adds agglutinant by membrane separation activated sludge process and after processing waste water in groove, by biomembrance process, the membrane separation water through described membrane separation activated sludge process solid-liquid separation is further processed, in described membrane separation activated sludge process, the biological treatment of the microorganism in active sludge and the solid-liquid separation process of separatory membrane are carried out in same described groove, in described biomembrance process, carried out a biological disposal upon by the microorganism be attached on carrier.
2. method of wastewater treatment according to claim 1, the BOD of described membrane separation water
5/ COD
crbelow 0.3.
3. method of wastewater treatment according to claim 1 and 2, described biomembrance process is biological activated carbon treatment method.
4. a method of wastewater treatment, uses the microbial film process water that reverse osmosis membrane or nano-filtration membrane filtration treatment are obtained by the method for wastewater treatment described in any one of claims 1 to 3.
5. method of wastewater treatment according to claim 4, carries out concentration to the condensed water produced by described filtration treatment.
6. a wastewater treatment equipment, it possesses film separated activated sludge treatment unit and biofilm treatment apparatus,
In described film separated activated sludge treatment unit, the biological treatment of the waste water that the microorganism in active sludge carries out and the solid-liquid separation process of separatory membrane are carried out in same groove,
In described biofilm treatment apparatus, carried out a biological disposal upon by the membrane separation water of solid-liquid separation in described film separated activated sludge treatment unit by the microorganism be attached on carrier,
Described film separated activated sludge treatment unit has the agglutinant adding set adding agglutinant in described groove.
7. according to the wastewater treatment equipment described in claim 6, the BOD of described membrane separation water
5/ COD
crbelow 0.3.
8. the wastewater treatment equipment according to claim 6 or 7, described biofilm treatment apparatus is biological activated carbon treatment device.
9. the wastewater treatment equipment according to any one of claim 6 ~ 8, described wastewater treatment equipment also possesses reverse osmosis membrane filtration device or nanofiltration membrane filter appts, and described reverse osmosis membrane filtration device or nanofiltration membrane filter appts carry out filtration treatment to microbial film process water treated in biofilm treatment apparatus.
10. wastewater treatment equipment according to claim 9, described wastewater treatment equipment also possesses evaporation concentration device, and described evaporation concentration device carries out concentration to the condensed water produced through described reverse osmosis membrane filtration device or nanofiltration membrane filter appts.
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| JP2003088885A (en) * | 2001-09-18 | 2003-03-25 | Ebara Corp | Method and apparatus for treating organic waste water |
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